CN113845612B - Preparation method of main catalyst, catalyst and application thereof - Google Patents
Preparation method of main catalyst, catalyst and application thereof Download PDFInfo
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- CN113845612B CN113845612B CN202010596861.6A CN202010596861A CN113845612B CN 113845612 B CN113845612 B CN 113845612B CN 202010596861 A CN202010596861 A CN 202010596861A CN 113845612 B CN113845612 B CN 113845612B
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- metal halide
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- catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 93
- 150000003624 transition metals Chemical class 0.000 claims abstract description 93
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 75
- -1 ether metal compound Chemical class 0.000 claims abstract description 67
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910001507 metal halide Inorganic materials 0.000 claims abstract description 33
- 150000005309 metal halides Chemical class 0.000 claims abstract description 33
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 28
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000007787 solid Substances 0.000 claims abstract description 27
- 239000003960 organic solvent Substances 0.000 claims abstract description 25
- 239000011541 reaction mixture Substances 0.000 claims abstract description 10
- 238000006722 reduction reaction Methods 0.000 claims abstract description 7
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical group NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 20
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 18
- KHCZSJXTDDHLGJ-UHFFFAOYSA-N 2,3,4,5,6-pentachloroaniline Chemical compound NC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl KHCZSJXTDDHLGJ-UHFFFAOYSA-N 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 14
- DADSZOFTIIETSV-UHFFFAOYSA-N n,n-dichloroaniline Chemical compound ClN(Cl)C1=CC=CC=C1 DADSZOFTIIETSV-UHFFFAOYSA-N 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 13
- KUDPGZONDFORKU-UHFFFAOYSA-N n-chloroaniline Chemical compound ClNC1=CC=CC=C1 KUDPGZONDFORKU-UHFFFAOYSA-N 0.000 claims description 11
- 229930195733 hydrocarbon Natural products 0.000 claims description 10
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- 125000005843 halogen group Chemical group 0.000 claims description 9
- KUWAAZMPJBFLEO-UHFFFAOYSA-N n,n,2-trichloroaniline Chemical compound ClN(Cl)C1=CC=CC=C1Cl KUWAAZMPJBFLEO-UHFFFAOYSA-N 0.000 claims description 9
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 9
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 claims description 4
- JDEJGVSZUIJWBM-UHFFFAOYSA-N n,n,2-trimethylaniline Chemical compound CN(C)C1=CC=CC=C1C JDEJGVSZUIJWBM-UHFFFAOYSA-N 0.000 claims description 4
- 125000002723 alicyclic group Chemical group 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000004711 α-olefin Substances 0.000 abstract description 25
- 239000011954 Ziegler–Natta catalyst Substances 0.000 abstract description 20
- 150000001336 alkenes Chemical class 0.000 abstract description 8
- 238000007334 copolymerization reaction Methods 0.000 abstract description 8
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 7
- 239000002685 polymerization catalyst Substances 0.000 abstract description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 49
- 238000006243 chemical reaction Methods 0.000 description 37
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 34
- 238000003756 stirring Methods 0.000 description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 26
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 26
- 238000006116 polymerization reaction Methods 0.000 description 24
- 238000002156 mixing Methods 0.000 description 21
- 229910052757 nitrogen Inorganic materials 0.000 description 19
- 238000001035 drying Methods 0.000 description 17
- 239000002245 particle Substances 0.000 description 16
- 238000009826 distribution Methods 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 12
- MYWQGROTKMBNKN-UHFFFAOYSA-N tributoxyalumane Chemical compound [Al+3].CCCC[O-].CCCC[O-].CCCC[O-] MYWQGROTKMBNKN-UHFFFAOYSA-N 0.000 description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 229910007926 ZrCl Inorganic materials 0.000 description 9
- IUFDZNVMARBLOJ-UHFFFAOYSA-K aluminum;quinoline-2-carboxylate Chemical compound [Al+3].C1=CC=CC2=NC(C(=O)[O-])=CC=C21.C1=CC=CC2=NC(C(=O)[O-])=CC=C21.C1=CC=CC2=NC(C(=O)[O-])=CC=C21 IUFDZNVMARBLOJ-UHFFFAOYSA-K 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 7
- 239000003638 chemical reducing agent Substances 0.000 description 7
- 230000010287 polarization Effects 0.000 description 7
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 235000012239 silicon dioxide Nutrition 0.000 description 6
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 5
- 229920000098 polyolefin Polymers 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 5
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 4
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 150000004820 halides Chemical class 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 229910003074 TiCl4 Inorganic materials 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000012718 coordination polymerization Methods 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000010687 lubricating oil Substances 0.000 description 2
- XDKQUSKHRIUJEO-UHFFFAOYSA-N magnesium;ethanolate Chemical compound [Mg+2].CC[O-].CC[O-] XDKQUSKHRIUJEO-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 2
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 235000011147 magnesium chloride Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 125000005493 quinolyl group Chemical group 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- QFCVQKSWGFVMTB-UHFFFAOYSA-N trihexoxyalumane Chemical compound [Al+3].CCCCCC[O-].CCCCCC[O-].CCCCCC[O-] QFCVQKSWGFVMTB-UHFFFAOYSA-N 0.000 description 1
- LIJDDOXRYWAXQG-UHFFFAOYSA-N tripentoxyalumane Chemical compound CCCCCO[Al](OCCCCC)OCCCCC LIJDDOXRYWAXQG-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/14—Monomers containing five or more carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/14—Monomers containing five or more carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
- C08F2410/03—Multinuclear procatalyst, i.e. containing two or more metals, being different or not
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The application discloses a preparation method of a main catalyst, the catalyst and application thereof, belonging to the field of olefin polymerization catalysts. The method comprises the following steps: 1) Obtaining a reaction mixture comprising an organic ether metal compound, a bond polarizing agent, and a transition metal halide in an inert organic solvent; 2) Adding a carbon material having a microporous structure to the reaction mixture obtained in 1); 3) Adding main group metal halide serving as a reducing aid into the mixture obtained in the step 2); 4) The temperature is increased to accelerate the reduction reaction to generate the low-valence transition metal halide, and the low-valence transition metal halide is loaded on a carbon material with a microporous structure to obtain the solid granular main catalyst. The main catalyst does not contain high-valence transition metal atoms, so that the Ziegler-Natta catalyst does not contain high-valence transition metal atoms, and can efficiently catalyze the homopolymerization and copolymerization of alpha-olefin.
Description
Technical Field
The application relates to the field of olefin polymerization catalysts, in particular to a preparation method of a main catalyst, a catalyst and application thereof.
Background
The high molecular weight alpha-olefin polymer is a material with excellent performance, is mainly used as a drag reducer, a lubricating oil tackifier and the like conveyed by a liquid oil pipeline, and can greatly improve the elastic transportation of the liquid oil pipeline, so that the contradiction between high yield and low transportation can be solved when the liquid oil pipeline runs at full load. Among them, high molecular weight α -olefin polymers are usually polymerized from α -olefins, and catalysts for catalyzing the polymerization of α -olefins are the core of the polymerization technology.
The related technology provides a Ziegler-Natta catalyst for catalyzing olefin polymerization and a preparation method thereof, and MgCl is supported 2 Dissolved in a mixture of an alcohol and an alkane to form liquid MgCl 2 Alcohol adduct, followed by addition of TiCl 4 So that the liquid MgCl 2 Alcohol adducts with TiCl 4 And fully contacting to obtain the Ziegler-Natta catalyst for catalyzing olefin polymerization.
However, the Ti contained in the Ziegler-Natta catalyst has a high valence state, that is, the valence state of Ti in the Ziegler-Natta catalyst is a quaternary valence state, and the quaternary valence state of Ti is advantageous for catalyzing the polymerization of ethylene and disadvantageous for catalyzing the polymerization of α -olefin, so the Ziegler-Natta catalyst cannot effectively catalyze the homopolymerization and copolymerization of α -olefin.
Disclosure of Invention
The application provides a preparation method of a main catalyst, the catalyst and application thereof, which can solve the problem that alpha-olefin cannot be efficiently catalyzed to generate homopolymerization and copolymerization in the related technology. The technical scheme is as follows:
in one aspect, a method for preparing a procatalyst is provided, the method comprising:
1) Obtaining a reaction mixture comprising an organic ether metal compound, a bond polarizing agent, and a transition metal halide in an inert organic solvent;
2) Adding a carbon material having a microporous structure to the reaction mixture obtained in 1);
3) Adding main group metal halide serving as a reducing assistant into the mixture obtained in the step 2);
4) The temperature is increased to accelerate the reduction reaction to generate the low-valence transition metal halide, and the low-valence transition metal halide is loaded on a carbon material with a microporous structure to obtain the solid granular main catalyst.
Optionally, the inert organic solvent is selected from C 5 ～C 20 Saturated hydrocarbon of (C) 5 ～C 20 Alicyclic hydrocarbon of (2), C 6 ～C 20 And/or C 3 ～C 20 Saturated heterocyclic hydrocarbons of (a).
Optionally, the molar ratio between the organic ether metal compound, the bond polarizer, the transition metal halide, the carbon material, and the main group metal halide is: 1: (0.01-1): (0.1-20): (5-30): (0.01-20).
Alternatively, the organic ether metal compound is selected from the group consisting of compounds of the formula Al (OR) 3 Wherein R is selected from C 1 ～C 20 Aliphatic hydrocarbon group of (2), C 3 ～C 20 Alicyclic group of or C 6 ～C 20 The aromatic group of (1).
Optionally, the bond polarizing agent is hexamethylenediamine, hexylamine, aniline, methylaniline, trimethylaniline, chloroaniline, dichloroaniline, trichloroaniline and/or pentachloroaniline.
Alternatively, the transition metal halide is selected from compounds of the formula M (R) 1 ) 4-m X m At least one of the compounds of (a), wherein M is Ti, zr or Hf; x is a halogen atom selected from Cl, br, F; m is an integer of 1 to 4; r 1 Is selected from C 1 ～C 20 Aliphatic hydrocarbon radical of (C) 1 ～C 20 The aromatic hydrocarbon group of (1).
OptionallyThe main group metal halide is selected from the group consisting of those of the general formula QX m At least one of the compounds of (1), wherein Q is a main group metal selected from Al, ca, ba, na or K; x is halogen selected from Cl, br or F; m is an integer selected from 3, 2 or 1.
In one aspect, there is provided a Ziegler-Natta catalyst comprising said procatalyst prepared according to any of the preceding claims, optionally said Ziegler-Natta catalyst further comprising a cocatalyst.
Optionally wherein the molar ratio of the transition metal halide in the procatalyst to said cocatalyst is from 1 (10-500), preferably said cocatalyst is an alkylaluminum compound, such as methylaluminoxane.
In one aspect, there is provided a process for the polymerization or copolymerization of alpha-olefins comprising the step of using any of the above Ziegler-Natta catalysts.
The technical scheme provided by the application can bring the following beneficial effects at least:
the carbon material with the micropore structure can provide a reaction site for reducing transition metal halide into low-valence transition metal halide, strong electronegative atoms in the bond polarization agent can generate coordination with transition metal atoms in the transition metal halide, so that the bond length between the transition metal atoms and halogen atoms in the transition metal halide is prolonged, polarization is enhanced, the transition metal atoms in the transition metal halide are further more easily reduced into the low-valence transition metal atoms, main group metal halide can be used as a reducing assistant to generate coordination polymerization with ether bonds in organic ether metal compounds, so that the organic ether metal compounds have higher reducibility, then the organic ether metal compounds with higher reducibility can be used as a reducing agent to reduce the transition metal halide into the low-valence transition metal halide, and the obtained low-valence transition metal halide can be deposited on the carbon material with the micropore structure in a solid form. Because the prepared main catalyst does not contain high-valence transition metal atoms, the Ziegler-Natta catalyst containing the main catalyst does not contain high-valence transition metal atoms, so that the Ziegler-Natta catalyst can efficiently catalyze alpha-olefin to carry out homopolymerization and copolymerization, and the molecular weight of an alpha-olefin polymer generated by polymerization can reach 35 to 1200 ten thousand.
Drawings
FIG. 1 is a schematic flow chart of a method for preparing a main catalyst according to an embodiment of the present disclosure.
Detailed Description
To make the objects, technical solutions and advantages of the present application more clear, embodiments of the present application will be described in further detail below with reference to the accompanying drawings.
FIG. 1 is a schematic flow chart of a method for preparing a main catalyst according to an embodiment of the present disclosure. Referring to fig. 1, the method comprises the steps of:
step 1: a reaction mixture is obtained comprising an organic ether metal compound, a bond polarizing agent, and a transition metal halide in an inert organic solvent.
The molar ratio of the organic ether metal compound, the bond polarizing agent and the transition metal halide is 1: (0.01-1): (0.1-20). Illustratively, the molar ratio between the organic ether metal compound, the bond polarizer, and the transition metal halide may be 1:0.01:0.1; the molar ratio between the organic ether metal compound, the bond polarizer and the transition metal halide may be 1:0.2:0.5; the molar ratio between the organic ether metal compound, the bond polarizer and the transition metal halide may also be 1:1:20.
the molar ratio among the organic ether metal compound, the bond polarizing agent, and the transition metal halide in the examples of the present application is not limited to these.
The inert organic solvent is a solvent which is used for dissolving the organic ether metal compound, the bond polarizing agent and the transition metal halide and does not undergo solvation with the organic ether metal compound, the bond polarizing agent and the transition metal halide during the dissolving process. In the embodiment of the present application, the type of the inert organic solvent can be selected according to the use requirement, for example, the inert organic solvent can be selected from C 5 ～C 20 Saturated hydrocarbon of (C) 5 ～C 20 Alicyclic hydrocarbon of (C) 6 ～C 20 Aromatic hydrocarbons of (2) and/or C 3 ～C 20 Saturated heterocyclic hydrocarbons of (4). Illustratively, the inert organic solvent may be C 5 ～C 20 The inert organic solvent may also be C 5 ～C 20 Saturated hydrocarbons of (2) and C 5 ～C 20 When the inert organic solvent is C 5 ～C 20 Saturated hydrocarbons and C 5 ～C 20 When two kinds of alicyclic hydrocarbons are mixed, the mixing ratio may be, for example, 1:1; the inert organic solvent may also be C 5 ～C 20 Saturated hydrocarbon of (C) 5 ～C 20 And C 6 ～C 20 When the inert organic solvent is C 5 ～C 20 Saturated hydrocarbon of (C) 5 ～C 20 And C 6 ～C 20 When three kinds of aromatic hydrocarbons are mixed, the mixing ratio may be, for example, 2:1:1; the inert organic solvent may also be C 5 ～C 20 Saturated hydrocarbon of (C) 5 ～C 20 Alicyclic hydrocarbon of (2), C 6 ～C 20 And C is an aromatic hydrocarbon 3 ～C 20 When the inert organic solvent is C 5 ～C 20 Saturated hydrocarbon of (C) 5 ～C 20 Alicyclic hydrocarbon of (2), C 6 ～C 20 And C is an aromatic hydrocarbon 3 ～C 20 In the case of mixing four kinds of saturated heterocyclic hydrocarbons, the mixing ratio may be, for example, 2:1:1:1.
the combination of the inert organic solvents in the embodiments of the present application is not limited to this, and the ratio of the combination of the components of the selected inert organic solvents is not limited to this.
Among them, the inert organic solvent may be preferably one of n-hexane, n-heptane, cyclohexane, toluene or hexane. The normal hexane, normal heptane, cyclohexane, toluene or hexane is a common inert organic solvent, so that the organic solvent can be purchased in the market, and the purchase cost is low.
The organic ether metal compound is a compound used as a main reducing agent for reducing a transition metal halide to a lower transition metal halide. In thatIn the embodiment of the present application, the type of the organic ether metal compound can be selected according to the use requirement, for example, the organic ether metal compound can be selected from the group consisting of compounds represented by the general formula Al (OR) 3 Wherein R may be selected from C 1 ～C 20 Aliphatic hydrocarbon group of (C) 3 ～C 20 Alicyclic group of or C 6 ～C 20 The aromatic group of (2). Illustratively, the organic ether metal compound may be aluminum triisopropoxide, aluminum tributoxide, aluminum tripentanolate, aluminum trihexanolate, aluminum tribenzylate, aluminum quinolinate, aluminum tricyclohexylate, or the like.
For example, the organic ether metal compound may be one of aluminum triisopropoxide, the organic ether metal compound may be one of aluminum tributoxide, and the organic ether metal compound may be one of aluminum quinolate. The organic ether metal compound may be a mixture of aluminum triisopropoxide and aluminum tributoxide, and when the organic ether metal compound is a mixture of aluminum triisopropoxide and aluminum tributoxide, the mixing ratio may be, for example, 1:1; the organic ether metal compound may also be a mixture of three kinds of aluminum triisopropoxide, aluminum tributoxide and aluminum quinolate, and when the organic ether metal compound is a mixture of three kinds of aluminum triisopropoxide, aluminum tributoxide and aluminum quinolate, for example, the mixing ratio may be 2:1:1; the organic ether metal compound may also be a mixture of four kinds of aluminum triisopropoxide, aluminum tributoxide, aluminum tribenzylate, and aluminum quinolinate, and when the organic ether metal compound is a mixture of four kinds of aluminum triisopropoxide, aluminum tributoxide, aluminum tribenzylate, and aluminum quinolinate, for example, the mixing ratio may be 2:1:1:1.
the combination of the organic ether metal compounds in the embodiments of the present application is not limited to this, and the ratio of the combination of the components of the organic ether metal compounds is not limited to this.
The bond polarizer is a reagent for increasing the bond length between the transition metal atom and the halogen atom in the transition metal halide to enhance polarization, thereby making it easier to reduce the transition metal atom in the transition metal halide to a lower transition metal. In the embodiment of the present application, the type of the key polarizer can be selected according to the use requirement, for example, the key polarizer can be C 5 To C 20 The organic amine of (2), further the bonding polarizer may be an aliphatic amine or an aromatic amine.
Among them, the bond polarizing agent may preferably be hexamethylenediamine, hexylamine, aniline, methylaniline, trimethylaniline, chloroaniline, dichloroaniline, trichloroaniline and/or pentachloroaniline. Since hexanediamine, hexylamine, aniline, methylaniline, trimethylaniline, chloroaniline, dichloroaniline, trichloroaniline and pentachloroaniline are common reagents, the reagent can be purchased in the market, and the purchase cost is low.
Illustratively, the bonding polarizing agent may be one of aniline, the bonding polarizing agent may be one of hexamethylene diamine, the bonding polarizing agent may be one of methylaniline, the bonding polarizing agent may be one of pentachloroaniline, the bonding polarizing agent may be one of dichloroaniline, the bonding polarizing agent may be one of chloroaniline, and the bonding polarizing agent may be one of trichloroaniline. The bond polarizing agent may be a mixture of two of aniline and hexamethylenediamine, and when the bond polarizing agent is a mixture of two of aniline and hexamethylenediamine, the mixing ratio may be, for example, 1:1; the bonding polarization agent may be a mixture of three of hexamethylene diamine, methylaniline and chloroaniline, and when the bonding polarization agent is a mixture of three of hexamethylene diamine, methylaniline and chloroaniline, the mixing ratio may be 2:1:1; the bond polarizing agent may also be four mixtures of chloroaniline, dichloroaniline, trichloroaniline and pentachloroaniline, and when the bond polarizing agent is four mixtures of chloroaniline, dichloroaniline, trichloroaniline and pentachloroaniline, for example, the mixing ratio may be 2:1:1:1.
the embodiment of the present application is not limited to the combination of the above-mentioned key polarizers, and the ratio between the selected combination of the components of the key polarizers is not limited to this.
It should be noted that the transition metal halide is a compound for providing a basic constituent component to the main catalyst. In the embodiment of the present application, the type of the transition metal halide may be selected according to the use requirement, for example, the transition metal halide may be selected from the group consisting of compounds of the general formula M (R) 1 ) 4-m X m At least one of the compounds of (a), wherein M is Ti, zr or Hf; x is a halogen atom selected from Cl, br,F; m is an integer of 1 to 4; r1 is selected from C 1 ～C 20 Aliphatic hydrocarbon radical of (C) 1 ～C 20 The aromatic hydrocarbon group of (1). Exemplary, R 1 May be at least one of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, isobutyl, tert-butyl, isopentyl, tert-pentyl, 2-ethylhexyl, phenyl, naphthyl, o-methylphenyl, m-methylphenyl, p-methylphenyl, o-sulfophenyl, formyl, acetyl, quinolyl or benzoyl.
Among them, as a preferable example, the transition metal halide may be TiCl 4 、ZrCl 4 、HfCl 4 、NiCl 2 、YCl 3 、ScCl 3 Or NdCl 3 And the like. Due to TiCl 4 、ZrCl 4 、HfCl 4 、NiCl 2 、YCl 3 、ScCl 3 Or NdCl 3 Is a common halide, so the halide can be purchased in the market, and the purchase cost is lower.
Illustratively, the transition metal halide may be TiCl 4 The transition metal halide can also be ZrCl 4 The transition metal halide may be NiCl 2 Alternatively, the transition metal halide may be YCl 3 Alternatively, the transition metal halide may be NdCl 3 Alternatively, the transition metal halide may be HfCl 4 The transition metal halide can also be ScCl 3 One kind of the method. The transition metal halide may also be TiCl 4 And ZrCl 4 Two kinds of mixture, when the transition metal halide is TiCl 4 And ZrCl 4 In the case of two kinds of mixing, the mixing ratio may be, for example, 1:1; the transition metal halide may also be ZrCl 4 、HfCl 4 And NiCl 2 Three kinds are mixed, when the transition metal halide is ZrCl 4 、HfCl 4 And NiCl 2 In the case of three kinds of mixing, the mixing ratio may be, for example, 2:1:1; the transition metal halide may also be NiCl 2 、YCl 3 、ScCl 3 And NdCl 3 Four mixtures, when the transition metal halide is NiCl 2 、YCl 3 、ScCl 3 And NdCl 3 In the case of four types of mixing, the mixing ratio may be, for example, 2:1:1:1.
the embodiment of the present application is not limited to the above combinations of transition metal halides, and the ratio of the selected combinations of transition metal halides is not limited to this.
Specifically, the operation of step 1 may be: the organic ether metal compound is dispersed in an inert organic solvent at a first predetermined temperature, followed by the addition of a bond polarizer and a transition metal halide, and stirring for a first predetermined time.
The first predetermined temperature is 0 to 50 ℃, for example, the first predetermined temperature may be 0 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃ or 50 ℃. The first predetermined time is 0.5 to 5 hours, for example, the first predetermined time may be 0.5 hour, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, or the like.
Alternatively, the inert organic solvent may be added to the reactor first, and then stirring in the above process may be achieved by providing a stirrer in the reactor, for example, a propeller stirrer, a paddle stirrer, a propeller stirrer, a turbine stirrer may be provided. The stirring in the above process can be achieved by manual stirring.
Step 2: a carbon material having a microporous structure is added to the reaction mixture obtained in step 1.
It should be noted that the carbon material having a microporous structure is used to provide a reaction site for the reduction of the transition metal halide to a lower transition metal halide, which is finally deposited on the surface of the carbon material in a solid form. The pore size of the microporous structure on the carbon material may be selected in advance according to the use requirement, for example, the pore size of the microporous structure may be 5 to 1500 micrometers, and for example, the pore size of the microporous structure may be 5 micrometers, 50 micrometers, 200 micrometers, 500 micrometers, 1000 micrometers, 1500 micrometers, or the like. The type of carbon material may also be pre-selected according to the use requirements, for example, the carbon material may be activated carbon, graphite or carbon.
The molar ratio between the organic ether metal compound and the carbon material having a microporous structure may be 1: (5-30). For example, the molar ratio between the organic ether metal compound and the carbon material having a microporous structure may be 1:5; the molar ratio between the organic ether metal compound and the carbon material having a microporous structure may be 1:10; the molar ratio between the organic ether metal compound and the carbon material having a microporous structure may also be 1:30.
in the examples of the present application, the molar ratio between the organic ether metal compound and the carbon material having a microporous structure is not limited to this.
Specifically, the operation of step 2 may be: adding a carbon material having a microporous structure to the reaction mixture obtained in the step 1, and stirring for a second preset time.
The second predetermined time is 0.5 to 5 hours, for example, the second predetermined time may be 0.5 hour, 1 hour, 2 hours, 3 hours, 4 hours, or 5 hours.
In addition, the stirring manner is the same as that in step 1, and the details of the embodiments of the present application are not described herein.
And step 3: a main group metal halide is added as a co-reductant after step 2.
It is noted that the main group metal halide acts as a co-reducing agent, which accelerates the reaction rate of the reduction of the transition metal halide to the lower valence transition metal halide. In the embodiments of the present application, the type of the main group metal halide can be selected according to the use requirement, for example, the main group metal halide can be selected from the group consisting of those with the general formula QX m At least one of the compounds of (1), wherein Q is a main group metal selected from Al, ca, ba, na or K; x is halogen selected from Cl, br or F; m is an integer selected from 3, 2 or 1.
Among them, the main group metal halide may be AlCl as a preferable choice 3 ，AlEt 2 Cl，AlEtCl 2 Or CaCl 2 And the like. Due to AlCl 3 ，AlEt 2 Cl，AlEtCl 2 Or CaCl 2 Is a common halide, so the halide can be purchased in the market and the purchase cost is lower.
Illustratively, the main group metal halide may be AlCl 3 The main group metal halide may be AlEt 2 The main group metal halide may also be AlEtCl, a Cl species 2 One kind of the medicine. The main group metal halide may also be AlCl 3 And AlEt 2 Cl, when the main group metal halide is AlCl 3 And AlEt 2 When two kinds of Cl are mixed, the mixing ratio may be, for example, 1:1; the main group metal halide may also be AlCl 3 ，AlEt 2 Cl and AlEtCl 2 Three kinds of mixed, when the main group metal halide is AlCl 3 ，AlEt 2 Cl and AlEtCl 2 In the case of three kinds of mixing, the mixing ratio may be, for example, 2:1:1; the main group metal halide may also be AlCl 3 ，AlEt 2 Cl，AlEtCl 2 And CaCl 2 Four kinds of mixed, when the main group metal halide is AlCl 3 ，AlEt 2 Cl，AlEtCl 2 And CaCl 2 In the case of four types of mixing, the mixing ratio may be, for example, 2:1:1:1.
the embodiment of the present application is not limited to the above combinations of the main group metal halides, and the ratio of the selected combinations of the main group metal halides is not limited to this.
The molar ratio between the organic ether metal compound and the main group metal halide may be 1: (0.01-20). Illustratively, the molar ratio between the organic ether metal compound and the main group metal halide may be 1:0.01; the molar ratio between the organic ether metal compound and the main group metal halide may be 1:10; the molar ratio between the organic ether metal compound and the main group metal halide may also be 1:20.
however, the molar ratio between the organic ether metal compound and the main group metal halide is not limited thereto in the examples of the present application.
Specifically, the operation of step 3 may be: after step 2, the main group metal halide is added to the reaction mixture and stirred for a third predetermined time.
The third predetermined time is 0.5 to 5 hours, for example, the third predetermined time may be 0.5 hour, 1 hour, 2 hours, 3 hours, 4 hours, or 5 hours.
In addition, the stirring manner is the same as that in step 1, and details are not repeated herein in the embodiments of the present application.
And 4, step 4: the temperature is increased to accelerate the reduction reaction to generate the low-valence transition metal halide, and the low-valence transition metal halide is loaded on a carbon material with a microporous structure to obtain the solid granular main catalyst.
It should be noted that the mixture undergoes a reduction reaction during the increase of the temperature to reduce the transition metal atom from a tetravalent or higher valence state to a lower valence state. Because the solubility of the low-valence transition metal halide in the inert organic solvent is low, solid particles are gradually precipitated, and the precipitated solid particles are loaded on a carbon material with a microporous structure, so that a solid granular main catalyst can be obtained. The preset temperature value that the temperature can be raised to can be set according to the use requirement, for example, the preset temperature value can be between 50 ℃ and 200 ℃. Illustratively, the preset temperature value may be 50 ℃, 85 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, or 200 ℃ or the like.
Specifically, the operation of step 4 may be: and (3) carrying out temperature raising operation on the mixture obtained in the step (3). When the temperature reaches a preset temperature value, the mixture is stirred so that the organic ether metal compound, the bond polarizing agent, the transition metal halide and the main group metal halide in the mixture are sufficiently reacted on the surface of the carbon material. After the fourth preset time of reaction, stopping stirring, and allowing the mixture to stand and filter to remove unreacted organic ether metal compound, bond polarization agent, transition metal halide and main group metal halide or inert organic solvent in the mixture. And drying the filtered mixture for a fifth preset time in a drying environment with a second preset temperature to obtain powdery solid particles.
The fourth predetermined time is 0.5 to 15 hours, for example, the second predetermined time may be 0.5 hour, 4 hours, 5 hours, 8 hours, 9 hours, 10 hours, or 15 hours. The second predetermined temperature is 30-130 deg.C, for example, the second predetermined temperature can be 30 deg.C, 40 deg.C, 45 deg.C, 50 deg.C, 55 deg.C, 40 deg.C or 130 deg.C. The fifth predetermined time is 0.5 to 5 hours, for example, the fifth predetermined time may be 0.5 hour, 2 hours, 2.5 hours, 3 hours, 4 hours, or 5 hours, etc.
In addition, the stirring manner is the same as that in step 1, and the details of the embodiments of the present application are not described herein.
In the embodiment of the present application, the carbon material with a microporous structure may provide a reaction site for reducing the transition metal halide to the low-valence transition metal halide, a strong electronegative atom in the bond polarizability agent may perform a coordination action with a transition metal atom in the transition metal halide, so that the bond length between the transition metal atom and a halogen atom in the transition metal halide is increased, polarization is enhanced, and the transition metal atom in the transition metal halide is further easily reduced to the low-valence transition metal atom, the main group metal halide may be used as a reducing assistant to perform coordination polymerization with an ether bond in the organic ether metal compound, so that the organic ether metal compound has higher reducibility, and then the organic ether metal compound with higher reducibility may be used as a reducing agent to reduce the transition metal halide to the low-valence transition metal halide, and the obtained low-valence transition metal halide may be deposited on the carbon material with a microporous structure in a solid form. Because the prepared main catalyst does not contain transition metal atoms with high valence, the catalyst is beneficial to catalyzing alpha-olefin polymerization by a Ziegler-Natta catalyst comprising the main catalyst at the later stage so as to obtain alpha-olefin polymerization products with high molecular weight. And the prepared main catalyst has good solid particle shape, is spherical, does not agglomerate and does not stick to walls. Meanwhile, the main catalyst has the advantages of simple preparation process, low cost, low equipment requirement, low energy consumption and low environmental pollution.
In a second aspect, the present examples provide a Ziegler-Natta catalyst comprising a procatalyst prepared as described above, optionally further comprising a cocatalyst.
It should be noted that the cocatalyst is a substance which is not active or has little activity by itself, but can change some properties of the Ziegler-Natta catalyst, such as chemical composition, ionic valence, acidity and alkalinity, surface structure, grain size, etc., so that the activity, selectivity, toxicity resistance or stability of the Ziegler-Natta catalyst is improved.
The type of cocatalyst can be chosen according to the needs of use, for example, the cocatalyst can be an alkylaluminum compound. As the cocatalyst, there may be exemplified those known in the art for olefin polymerization, i.e., organoaluminum compounds.
Among them, as a preferable example, the cocatalyst may be triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, diethylaluminum monochloride, methylaluminoxane, etc. Because triethyl aluminum, triisobutyl aluminum, tri-n-hexyl aluminum, diethyl aluminum monochloride and methylaluminoxane are common cocatalysts, the cocatalysts can be purchased in the market, and the purchase cost is low.
Alternatively, wherein the molar ratio between the transition metal halide in the main catalyst and the cocatalyst can be 1: (10-500). Illustratively, the molar ratio may be 1:10; the molar ratio may be 1:30, of a nitrogen-containing gas; the molar ratio may also be 1:500.
in the embodiments of the present application, the molar ratio between the transition metal halide and the cocatalyst in the main catalyst is not limited to this.
In the embodiment of the application, the activity of the Ziegler-Natta catalyst is high because the main catalyst of the Ziegler-Natta catalyst does not contain a transition metal atom with a high valence state, so that the polymerization or copolymerization of alpha-olefin can be efficiently catalyzed by the Ziegler-Natta catalyst.
In a third aspect, the present embodiments provide a method of polymerizing or copolymerizing an alpha-olefin comprising the step of using the above-described Ziegler-Natta catalyst.
It should be noted that the type of alpha-olefin can be selected according to the application requirements, for example, the alpha-olefin can be selected from C 3 ～C 20 The olefin of (1). Illustratively, the α -olefin may be propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 3-methyl-1-butene, cyclopentene, 4-methyl-1-pentene, 1, 3-butadiene, isoprene, norbornene, a non-conjugated diene, styrene, methylstyrene, or the like.
In addition, when the alpha-olefin is polymerized or copolymerized, the reaction conditions of the polymerization or copolymerization, i.e., the reaction temperature, the reaction time and the reaction pressure, can be set according to the use requirements. For example, the reaction temperature may be between-50 ℃ and 110 ℃, and illustratively, the reaction temperature may be-50 ℃, -15 ℃, -10 ℃, 0 ℃, 5 ℃, or 110 ℃, or the like. The reaction time may be between 0.5 and 240 hours, and illustratively, the reaction time may be 0.5 hour, 8 hours, 96 hours, 120 hours, 230 hours, 240 hours, or the like. The reaction pressure may be between 0.1 and 10 mpa, and illustratively, the reaction pressure may be 0.1 mpa, 1 mpa, 5 mpa, or 10 mpa, or the like.
In the embodiment of the application, the Ziegler-Natta catalyst is suitable for polymerizing or copolymerizing alpha-olefin in a bulk polymerization process, a slurry polymerization process, a gas-phase polymerization process or a combined polymerization process, and the obtained alpha-olefin polymer has high molecular weight and wide molecular weight distribution range of between 35 and 1200 ten thousand, so that the obtained alpha-olefin polymer can be used as a viscosity increaser of lubricating oil with excellent performance, a drag reducer conveyed by a liquid oil pipeline and the like.
In order to make the technical solutions and advantages of the present application more clear, the following detailed description will be given by means of alternative embodiments.
Example 1
This example provides a process for the preparation of a procatalyst by charging 5ml of TiCl at 30 ℃ in a reactor fully purged with nitrogen 4 0.5g of aluminum isopropoxide and 0.1g of aniline were added to 20ml of n-hexane, and stirred for 1 hour to obtain a mixture. 6g of activated carbon were then added to the mixture, the mixture was stirred for 1 hour, and 5g of AlCl were then added 3 And stirred for 0.5 hour. The temperature was then raised to 110 ℃, the mixture was stirred and TiCl in the mixture was allowed to form 4 Aluminum isopropoxide, aniline and AlCl 3 And reacting for 4h. Then, the stirring was stopped, and the mixture after the reaction was allowed to stand, separated into layers, and filtered. And then drying the catalyst for 2 hours in a vacuum environment at 50 ℃ to obtain the spherical powdery solid main catalyst with good fluidity and uniform particle size distribution.
Example 2
This example provides a process for the preparation of a procatalyst by charging 10ml of TiCl at 20 ℃ in a reactor which is fully purged with nitrogen 4 1g of aluminum isopropoxide and 0.5g of hexamethylenediamine were added to 30ml of n-hexane, and stirred for 0.5 hour to obtain a mixture. 6g of activated carbon are then added to the mixture, stirred for 0.5 hour, and 2g of AlCl are then added 3 And stirred for 1 hour. Then the temperature is raised to 120 ℃, the mixture is stirred and TiCl in the mixture is caused to react 4 Aluminum isopropoxide, hexamethylenediamine and AlCl 3 And reacting for 5 hours. Then, the stirring was stopped, and the mixture after the reaction was allowed to stand, separated into layers, and filtered. And then drying the catalyst for 2.5 hours in a vacuum environment at 40 ℃ to obtain the spherical powdery solid main catalyst with good fluidity and uniform particle size distribution.
Example 3
This example provides a process for the preparation of a procatalyst by charging 8ml of TiCl at 35 ℃ in a reactor fully purged with nitrogen 4 1.5g of aluminum tributoxide and 1g of methylaniline were added to 20ml of n-heptane, and stirred for 0.5 hour to obtain a mixture. Then 10g of graphite was added to the mixture, and the mixture was stirred for 0.5 hour, after which 2mL of AlEt was added 2 Cl (2.5M in hexane), stirred for 0.5 h. The temperature was then raised to 85 ℃ and the mixture was stirred and the TiCl4, aluminum tributoxide, methylaniline and AlEt were allowed to stand 2 Cl was reacted for 8h. Then, the stirring was stopped, and the mixture after the reaction was allowed to stand, separated into layers, and filtered. And then drying the catalyst for 2.5 hours in a vacuum environment at the temperature of 55 ℃, thereby obtaining the spherical powdery solid main catalyst with good fluidity and uniform particle size distribution.
Example 4
This example provides a process for the preparation of a procatalyst by charging 20ml of TiCl at 40 ℃ in a reactor fully purged with nitrogen 4 1.5g of aluminum quinolate and 1.2g of pentachloroaniline were added to 25ml of cyclohexane, and stirred for 1 hour to obtain a mixture. Then 10g of carbon were added to the mixture, stirred for 0.5 h, and then 1mL of AlEtCl was added 2 (2.5M in hexane), and stirred for 0.5 hour. Then raising the temperatureThe mixture is stirred at a temperature of between 100 ℃ and TiCl4, aluminum quinolate, pentachloranilide and AlEtCl in the mixture are obtained 2 And reacting for 10 hours. Then, the stirring was stopped, and the mixture after the reaction was allowed to stand, separated into layers, and filtered. And then drying the catalyst for 3 hours in a vacuum environment at the temperature of 45 ℃, thereby obtaining the spherical powdery solid main catalyst with good fluidity and uniform particle size distribution.
Example 5
This example provides a process for preparing a procatalyst by placing 5g of ZrCl in a reactor sufficiently purged with nitrogen at 20 deg.C 4 1.5g of aluminum triisopropoxide and 2g of dichloroaniline were added to 25ml of toluene, and stirred for 1 hour to obtain a mixture. Then 5g of activated carbon were added to the mixture, stirred for 0.5 hour, and then 1g of AlCl was added 3 And stirred for 0.5 hour. The temperature was then raised to 90 ℃, the mixture was stirred and ZrCl in the mixture was allowed to form 4 Aluminum triisopropoxide, dichloroaniline and AlCl 3 And reacting for 9h. Then, the stirring was stopped, and the mixture after the reaction was allowed to stand, separated into layers, and filtered. And then drying for 4 hours in a vacuum environment at 45 ℃ to obtain the spherical powdery solid main catalyst with good fluidity and uniform particle size distribution.
Example 6
This example provides a preparation method of main catalyst, in which 3g of NiCl is placed in a reactor fully substituted by nitrogen at 20 deg.C 2 1.5g of aluminum triisopropoxide and 3g of chloroaniline were added to 25ml of hexane and stirred for 1 hour to obtain a mixture. Then 6g of activated carbon were added to the mixture, stirred for 0.5 hour, and then 1g of AlCl was added 3 And stirred for 0.5 hour. The temperature was then raised to 90 ℃, the mixture was stirred and the NiCl in the mixture was allowed to stand 2 Aluminum triisopropoxide, chloroaniline and AlCl 3 And reacting for 8 hours. Then, the stirring was stopped, and the mixture after the reaction was allowed to stand, separated into layers, and filtered. And then drying for 4 hours in a vacuum environment at 40 ℃ to obtain the spherical powdery solid main catalyst with good fluidity and uniform particle size distribution.
Example 7
This embodiment is carriedA process for preparing the main catalyst is provided, in which 3g of YCl are introduced at 20 ℃ in a reactor which has been fully replaced by nitrogen 3 1.5g of aluminum tributoxide and 0.2g of dichloroaniline were added to 25ml of hexane and stirred for 1 hour to obtain a mixture. Then 5g of activated carbon was added to the mixture, and the mixture was stirred for 0.5 hour, followed by addition of 1.5g of AlEt 2 Cl, stirred for 0.5 hours. Then the temperature was raised to 90 ℃, the mixture was stirred and the YCl in the mixture was brought to 3 Aluminum tributyl oxide, dichloroaniline and AlEt 2 Cl was reacted for 8h. Then, the stirring was stopped, and the mixture after the reaction was allowed to stand, separated into layers, and filtered. And then drying for 4 hours in a vacuum environment at 40 ℃, thereby obtaining the spherical powdery solid main catalyst with good fluidity and uniform particle size distribution.
Example 8
This example provides a method for preparing a procatalyst by charging 20mL of TiCl at 25 deg.C in a reactor fully purged with nitrogen 4 2.5g of aluminum triisopropoxide and 0.5g of dichloroaniline were added to 1ml of hexane, and stirred for 1 hour to obtain a mixture. Then, 5g of activated carbon was added to the mixture, and the mixture was stirred for 0.5 hour, followed by addition of 1.5g of AlEt 2 Cl, stirred for 0.5 hours. The temperature is then raised to 100 ℃, the mixture is stirred and TiCl in the mixture is caused to form 4 Aluminum triisopropoxide, dichloroaniline and AlEt 2 Cl was reacted for 8h. Then, the stirring was stopped, and the mixture after the reaction was allowed to stand, separated into layers, and filtered. And then drying for 4 hours in a vacuum environment at 40 ℃, thereby obtaining the spherical powdery solid main catalyst with good fluidity and uniform particle size distribution.
Example 9
This example provides a method for preparing a procatalyst by charging 20mL of TiCl at 25 ℃ in a reactor purged well with nitrogen 4 2.5g of aluminum triisopropoxide and 0.5g of pentachloroaniline were added to 0.5ml of hexane and stirred for 1 hour to obtain a mixture. Then 15g of activated carbon was added to the mixture and stirred for 0.5 hour, after which 5.5g of AlCl was added 3 And stirred for 0.5 hour. Then the temperature is raised to 100 ℃, the mixture is stirred and mixedTiCl in the composition 4 Aluminum triisopropoxide, pentachloroaniline and AlCl 3 And reacting for 8 hours. Then, the stirring was stopped, and the mixture after the reaction was allowed to stand, separated into layers, and filtered. And then drying for 4 hours in a vacuum environment at 40 ℃ to obtain the spherical powdery solid main catalyst with good fluidity and uniform particle size distribution.
Example 10
This example provides a process for the preparation of a procatalyst by charging 5g of NdCl in a reactor fully purged with nitrogen at 25 deg.C 3 2.5g of aluminum triisopropoxide and 0.5g of pentachloroaniline were added to 25ml of hexane, and stirred for 1 hour to obtain a mixture. Then 10g of activated carbon was added to the mixture, and the mixture was stirred for 0.5 hour, after which 5.5g of AlCl was added 3 And stirred for 0.5 hour. The temperature is then raised to 100 ℃, the mixture is stirred and the NdCl in the mixture is brought to 3 Aluminum triisopropoxide, pentachloroaniline and AlCl 3 And reacting for 8 hours. Then, the stirring was stopped, and the mixture after the reaction was allowed to stand, separated into layers, and filtered. And then drying for 4 hours in a vacuum environment at 40 ℃ to obtain the spherical powdery solid main catalyst with good fluidity and uniform particle size distribution.
Example 11
This example provides a process for the preparation of a procatalyst by placing 5g of HfCl in a reactor sufficiently purged with nitrogen at 25 deg.C 4 2.5g of aluminum triisopropoxide and 0.1g of pentachloroaniline were added to 20ml of hexane, and stirred for 1 hour to obtain a mixture. Then 15g of activated carbon was added to the mixture, and the mixture was stirred for 0.5 hour, after which 5.5g of AlCl was added 3 And stirred for 0.5 hour. The temperature was then raised to 100 ℃, the mixture was stirred and HfCl in the mixture was allowed to form 4 Aluminum triisopropoxide, pentachloroaniline and AlCl 3 And reacting for 8 hours. Then, the stirring was stopped, and the mixture after the reaction was allowed to stand, separated into layers, and filtered. And then drying for 4 hours in a vacuum environment at 40 ℃ to obtain the spherical powdery solid main catalyst with good fluidity and uniform particle size distribution.
Example 12
The embodiment providesThe preparation method of the main catalyst comprises the steps of adding 5g of ScCl into a reactor which is fully replaced by nitrogen at 25 DEG C 3 2.5g of aluminum triisopropoxide and 0.3g of trichloroaniline were added to 20ml of hexane and stirred for 1 hour to obtain a mixture. Then, 15g of activated carbon was added to the mixture, and the mixture was stirred for 0.5 hour, followed by addition of 5.5g of AlEt 2 Cl, stirred for 0.5 h. The temperature was then raised to 100 ℃, the mixture was stirred and the ScCl in the mixture was allowed to settle 3 Aluminum triisopropoxide, trichloroaniline and AlEt 2 Cl reacted for 8h. Then, the stirring was stopped, and the mixture after the reaction was allowed to stand, separated into layers, and filtered. And then drying for 4 hours in a vacuum environment at 40 ℃ to obtain the spherical powdery solid main catalyst with good fluidity and uniform particle size distribution.
Comparative example 1
In a reactor which was sufficiently replaced with nitrogen, 1g of silicon dioxide was added to 20ml of decane, followed by stirring and raising the temperature to 110 ℃ to allow the silicon dioxide and decane to react for 2 hours, after the silicon dioxide was completely dissolved to form a solution, the temperature was lowered to 50 ℃, and 0.3ml of tetraethyl silicate was added to allow the solution and tetraethyl silicate to react for 2 hours. Then, the temperature of the solution system after the reaction is reduced to-15 ℃, 25ml of titanium tetrachloride is dripped in, the reaction is continued for 1 hour, and then the temperature is increased to 90 ℃ for reaction for 2 hours. And then stopping stirring, standing the solution system after reaction, layering, filtering, washing four times by adopting 30ml of hexane, and drying for 2 hours in a vacuum environment at the temperature of 80 ℃ to obtain a powdery solid main catalyst with better fluidity.
Comparative example 2
In a reactor which is fully replaced by nitrogen, 1g of magnesium dichloride is added into 20ml of decane, 6.5ml of isooctanol is added, then stirring and raising the temperature to 110 ℃ are carried out, so that silicon dioxide, decane and isooctanol react for 2h, after silicon dioxide is completely dissolved to form a solution, the temperature is reduced to 50 ℃, 0.3ml of tetraethyl silicate is added, and the solution reacts with the tetraethyl silicate for 2h. Then, the temperature of the solution system after the reaction is reduced to-15 ℃, 25ml of titanium tetrachloride is dripped in, the reaction is continued for 1 hour, and then the temperature is increased to 90 ℃ for reaction for 2 hours. And then stopping stirring, standing the solution system after reaction, layering, filtering, washing four times by adopting 30ml of hexane, and drying for 2 hours in a vacuum environment at the temperature of 80 ℃ to obtain a powdery solid main catalyst with better fluidity.
Comparative example 3
In a reactor which is fully replaced by nitrogen, 1g of diethoxymagnesium is added into 20ml of decane, 3.5ml of isooctanol is added, then stirring and raising the temperature to 100 ℃ are carried out, so that diethoxymagnesium, decane and isooctanol react for 2h, after silicon dioxide is completely dissolved to form a solution, the temperature is reduced to 50 ℃, 0.3ml of tetraethyl silicate is added, and the solution and tetraethyl silicate react for 2h. Then, the temperature of the solution system after the reaction is reduced to-15 ℃, 35ml of titanium tetrachloride is dripped in, the reaction is continued for 1 hour, and then the temperature is increased to 90 ℃ for reaction for 2 hours. And then stopping stirring, standing the solution system after reaction, layering, filtering, washing four times by using 30ml of hexane, and drying for 2 hours in a vacuum environment at the temperature of 80 ℃ to obtain the powdery solid main catalyst with better fluidity.
Among them, the component composition ratios of the main catalysts prepared in examples 1 to 12 and comparative examples 1 to 3 are shown in table 1.
TABLE 1% Al and transition metals in the procatalyst
Application example 1
The polymerization of octenes was catalyzed by using the main catalysts prepared in examples 1 to 12 and comparative examples 1 to 3, respectively, as main catalysts in Ziegler-Natta catalysts by sequentially adding 20ml of octenes, 20mg of the main catalyst component and 1.5ml of the cocatalyst AlEt to a 300ml glass reactor fully substituted with nitrogen 3 The solution (2 mmol/ml) was used to catalyze polymerization of octene at a temperature of 0 deg.C for 96 hours.
Application example 2
As Ziegler catalysts, the main catalysts prepared in examples 1 to 12 and comparative examples 1 to 3 were used, respectivelyPolymerization of hexene catalyzed by the procatalyst of the Natta catalyst, the procedure may be to add 25ml of hexene, 20mg of the procatalyst component and 1.3ml of the cocatalyst AlEt in sequence to a 300ml glass reactor fully purged with nitrogen 3 The solution (2 mmol/ml) was used to catalyze the polymerization of hexene at a temperature of-10 ℃ for 8 hours.
Application example 3
The polymerization of decene was catalyzed by using the main catalysts prepared in examples 1 to 12 and comparative examples 1 to 3 as main catalysts in Ziegler-Natta catalysts, and specifically, 30ml of decene, 25mg of the main catalyst component and 1.2ml of the cocatalyst AlEt were sequentially added to a 300ml glass reactor fully substituted with nitrogen 3 The solution (2 mmol/ml) was polymerized at-15 deg.C for 230 hours.
Application example 4
The main catalysts prepared in examples 1 to 12 and comparative examples 1 to 3 were used as main catalysts in Ziegler-Natta catalysts to catalyze mixed olefins for polymerization, and the specific procedure was to sequentially add 15ml of octene, 15ml of hexene, 10ml of decene, 30mg of main catalyst component and 1.2ml of co-catalyst AlEt to a 300ml glass reactor fully purged with nitrogen 3 The solution (2 mmol/ml) was polymerized at 5 ℃ for 120 hours with catalysis of the mixed olefin.
The results of catalytic polymerization in application examples 1 to 4 are shown in Table 2.
TABLE 2 catalytic polymerization results
As can be seen from Table 2, the polymerization of alpha-olefins catalyzed by the procatalysts prepared in examples 1 to 12 as the procatalyst in a Ziegler-Natta catalyst has a high conversion of alpha-olefins during polymerization and the viscosity average molecular weight of the resulting polymers is also high, thus indicating that the procatalysts prepared in examples 1 to 12 do not contain high-valence transition metal atoms and can efficiently catalyze the homopolymerization and copolymerization of alpha-olefins.
The above description is intended only to illustrate the alternative embodiments of the present application, and should not be construed as limiting the present application, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (2)
1. A method of preparing a procatalyst, the method comprising:
1) Obtaining a reaction mixture comprising an organic ether metal compound, a bond polarizing agent, and a transition metal halide in an inert organic solvent;
2) Adding a carbon material having a microporous structure to the reaction mixture obtained in 1);
3) Adding main group metal halide serving as a reducing assistant into the mixture obtained in the step 2);
4) Raising the temperature to accelerate the reduction reaction to generate low-valence transition metal halide, wherein the low-valence transition metal halide is loaded on a carbon material with a microporous structure to obtain a solid granular main catalyst;
the organic ether metal compound is selected from the group consisting of compounds of the general formula Al (OR) 3 Wherein R is selected from C 1 ～C 20 Aliphatic hydrocarbon group of (2), C 3 ～C 20 Alicyclic group of or C 6 ～C 20 An aromatic group of (a);
the bond polarizing agent is hexamethylene diamine, hexylamine, aniline, methylaniline, trimethylaniline, chloroaniline, dichloroaniline, trichloroaniline and/or pentachloroaniline;
the transition metal halide is selected from the group consisting of M (R) 1 ) 4-m X m At least one of the compounds of (a), wherein M is Ti, zr or Hf; x is a halogen atom selected from Cl, br, F; m is an integer of 1 to 4; r 1 Is selected from C 1 ～C 20 Aliphatic hydrocarbon radical of (C) 1 ～C 20 An aromatic hydrocarbon group of (1);
the main group metal halide is selected from the group consisting of those having the general formula QX n At least one of the compounds of (1), wherein Q is a main group metal selected from Al, ca, ba, na or K; x is halogen selected from Cl, br or F; n is an integer selected from 3, 2 or 1;
the molar ratio between the organic ether metal compound, the bond polarizer, the transition metal halide, the carbon material, and the main group metal halide is 1: (0.01-1): (0.1-20): (5-30): (0.01-20).
2. The process of claim 1, wherein the inert organic solvent is selected from the group consisting of C 5 ～C 20 Saturated hydrocarbon of (C) 5 ～C 20 Alicyclic hydrocarbon of (2), C 6 ～C 20 And/or C 3 ～C 20 Saturated heterocyclic hydrocarbons of (4).
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